Time- and frequency-resolved spontaneous emission as a probe of coherence effects in ultrafast electron transfer reactions

We present results from quantum dynamical simulations of electron transfer, obtained using a multilevel version Redfield relaxation theory, which illustrate the complex dynamics that result when electron tunneling and vibrational relaxation processes occur on similar time scales. By treating the system-field interaction quantum mechanically, we examine the extent to which the time- and frequency-resolved emission signal reflects the electron transfer dynamics. The results from these simulations provide new insight into the role of quantum coherences in ultrafast rate processes and time-resolved spectral measurements.